Method of drying fluids



. MONOHYDRATED Marh12,194o. M YQSEATQN .l 2,193,570:

METHOD OF DRYING FLUIDS Filed July 22, 1939 NaOH soL'n 78 LEVEL OF @CLL BODIES OF .NaOH

@2W kme `-innemen Mar. 12, 1940 lUNITED oSTATESv PATENT `oFFlcl-z y I Miatello!) ozllisnsic lFLUIDS A. I I

Max Y. Seaton,V Greenwich, Conn., assignor to Westvaco Chlorine Products Corporation, New York, N. Y., a corporation of -Dlelaware Application July' 22, 1939, serial No. 286,039

r 'z (cl. 20o- 104) This invention or discovery relates to methods of dryingfiuids; and it comprises a. methodof drying a moist uid, (liquid or gas) which is inert with respect to NaOH, including the step of passing the moist fluid past extensive surfaces of solid hydrated caustic soda corresponding approximately to NaOHI-IiO, `advantageously in an elongated coniined zone, and removing causticliquor as formed, by gravitational action., to expose Vll) fresh surfaces of'NaOHHiO to the passing fluid;

all as more fully hereinafter set forthjand as claimed. d

Caustic soda, NaOH, lis theoretically an excellent drying agent in the sense that it is capable of l5 withdrawing water quite completely from nonreactive gasesand non-aqueous liquids in contact therewith. It-is, howevendiicult to utilize it as a drying'agent in anypractical way. `Eiiicient drying of a flowing current ofliquid or gas by any drying agent requires that extensive active surfaces be presented to the fluid flow' throughout the operation. Anhydrous NaOH swells when it takes up water, and commercial forms of solid anhydrous NaOH such as sticks, flakes and balls tend to cake as .they take up moisture, thereby l partly satisfied with a certain amount of water,

l that is a hydrated form of caustic sodacontain- 40 ing about 30 per cent H2O of crystallization, will reduce the partial pressure of H2O in gases to practically the same low point as anhydrous caustic, but presents great practical advantages in use in that the active surfaces are,so to speak,

.45 self-cleaning. The water taken up drip or drains away as a fluent soda solution of maximum Y concentration (at the drying temperature em.

ployed) and minimum vapor tension.

Commercial '70 per cent caustic, a solid material 50 melting at about 65 C., correponds substantiallyto the mono-hydrate NaOHHaO and is usefulfor the present purposes. It is commercially available in molten or semi-moltenv form, being often shippedpin tank cars fitted with heating coils to 55 permit melting and pumping.

In another and copendingl application` Serial No. 105,576, filed Oct. 14, 1936, for Methods of and apparatus for drying,l wherewith the present application contains matter in common, I have described and claimed utilization of these prop- '5 Aerties of mono-hydrate by supporting the monor hydrate in thinfilms or layers on solid bodies," such'as Raschig rings. In that embodiment of `my invention there are manypractical advantages, among them being that of regeneration by 10 running molten mono-hydrate down a tower containing packing materials such as Raschig rings. The excess of-mono-hydrate drips away leaving` the rings covered with a thin lm. The melting temperature being around 70, when the tower is 15 cooled below this temperature, the liquid films on the supporting bodies solidify. The active surface of the mono-hydrate can thus be maintained substantially constant in area. i

I have found that, in addition tousing caustic '20 soda mono-hydrate inthe formof thin lm's or layers on suitable supports, as described in the acknowledged application, it also serves as an excellent drying material when in the form of other shaped bodies. Shaped bodies of the mono- -25 hydrate which are suitable for the invention in.

cludes sticks, lumps, "balls, blocks, octahedrons, hexahedrons, etc. Octaliedral blocks tumbled 4 into a tower in random arrangement give a large v amount of caustic soda and at the same time provide extensive exposed surfaces and' an easily permeable assemblage for passing fluid.

' In use, theshaped bodies of caustic vmono- .hydrate are advantageously arranged as a permeable column in a tower or other suitable container. 'I'he bodies are conveniently supported on a "foraminous base, with fluid space above and below the column. The conduit connections to 'the tower depend on the character of the fluid to be dried. If the material Vbeing dried is a heavy 40 liquid. -that is one -having a specific gravity I greater than that of strong caustic solutions generally about 1,5) the liquid is conveniently introduced at the top of the column and is caused to pass down through the column p hydrate surfaces and out at the bottom. As the mono-hydrate surfaces take Aup water withA liquefaction, the resulting caustic solution tends to lrise through the heavier liquid, and may be conveniently drawn on at the top. The liquid being dried and the caustic solution formed thus move in ountercurrent. It is desirable to have the tower sumciently large in cross section to afford a reasonably slow linear rate of flow, so that the separation willtake place readily. On the other the mono- 45 i than the caustic solutions formed, or is a gas, it is introduced into the bottom of the tower and removed at the top. The caustic liquor as formed then drips or drains downward, and is'rernoved from the base of the tower.

The described process is particularly, useful hyrocarbons, which often contain a little HCl,

-that they are inert to caustic soda.

there is enough water in the liquefying monohydrated alkali to dissolve any salt (NaCl) which is formed by neutralization of the HC1; there is no glazing of the mono-hydrated caustic by a salt film, which sometimes causes difficultyV in drying with anhydrous caustic. The invention Ais also useful in drying such light liquids as gasoline and petroleum oils; these being introduced at the bottom of a column of monohydrate for upward flow. And as stated, the invention is useful in drying all sorts of gases, provided only Air and hydrogen are two gases to which the invention can be applied with particular advantage. It has been found lin practice that the mono-hydratev will reduce the partial pressure of H2O in gases furtherthan is possible with calcium chloride and most of the other ordinary drying agents. Indrying air, CO2 is also removed but this does not complicate the described operation. 'I'he amount of CO2 in ordinary air is very small compared to the moisture content, and there is enough water in the mono-hydrate to take care of sodium carbonate formed. f

The mono-hydrate can be used in the form of bodies of any suitable shape, for example, spheres, cyclinders or rods. Irregular shapes can vbe employed. It is best to have the bodies all substantially the same size, as this gives maximum permeability. Bodies from 1A; inch to 21/2 inches in average' diameter are convenient, depending on the size of the drying unit. The mono-hydrated caustic has a melting point so low that it is a simple matter to forrn the mono-hydrate into suitable shapes, by extrusion methods or b yrcasting'.

In the coursee ofV operation of a tower filled with shaped bodiesfof mono-hydrate, the bodies tend'to decrease in size, but there is little tendency to clump together as an impermeable mass because the surfaces of the bodies are always being 'renewed by withdrawal of thel liquefied caustic. Mono-hydrated caustic does not swell much on taking up water. and any possibledifficulty 'from swelling is obviated by liquecation of the surface layer as soon as water is absorbed.

The .charge in the tower is renewed from time f to time by introducing more of the bodies.

The hydrated caustic soda employed need not be exactly the mono-hydrate `(69 per cent NaOH and 3l per cent H2O) Hydratedforms of caustic soda'containing about 66 to 80 per cent NaOH and about 34 to 20 per cent water oi crystallization are useful, and are included in the term mono-hydrate as sometimes -uscd herein. These compounds have melting points of about 60 to 80 C; a value far below that of anhydrous caustic, which is 318 C. -As stated, hydrated? caustic loda having. melting points in this range Adesired shapes by very simple me coming dried in the process. :Dried CCl4 is` hand, if the material being dried is a liquid lighter is readily fusible and can be forged into the ods.

In the accompanying drawing, I have shown, more or less diagrammatically, three forms of apparatus useful in the performance of the described method. In the drawing,

Fig. 1.shows in vertical section a form paratus' useful in drying denseliquids);

Fi'g. 2 shows in vertical section 'a formof apparatus useful in drying light liquids andgases, and

Fig.'3 shows in vertical section a modied form of apparatus useful in drying heavy liquids, such as carbon tetrachloride. j

Referring to the drawing and in particular to Fig. 1, a casing I0 is provided of material resistant to caustic alkali and to the fluid being dried. A collection of shaped bodies Il (shown as spheres) of substantially mono-hydrated NaOH is provided in the casing, supported on a'foraminous plate I2 spaced above the casing bottom to leave'a reservoir.. space I3. A heavy liquid to bedried, such as CCh, is introduced at the top through a distributor I4 and flows downwardly through the mono-hydrate bodies, be-

of apremoved through a pipe I5, which advantage' ously has a bend I6 provided at such-height as to maintain the mono-hydrate column submerged in C014. As the surfaces of the mono- 30 hydrate bodies liquefy, the solution at' a density of about 1 .5 nds its way upwardly through the column and floats on top of the CC14 at I1.. The spent caustic is removed by a conduit I8 as shown. Separation is sharp and clean. The

CC14 is not conta/minated with NaOH, nor does the spent caustic liquor carryaway CC14. The apparatus is recharged with mono-hydrate bodies from time .to timethrough a manhole I9.

Nickel-clad steel or other material .resistant to 40 .caustic soda is advantageously employed in the construction of apparatus for practicing the invention. I

Referring to Fig. 2,`\a casing 22 is provided having a foraminousplate I2 spaced above the 45 bottom as in Fig. 1, and supporting a charge of monohydrate bodies 23, shown as cylinders. The casing has a detachable cover 24 for recharging. Gas or a light liquid to be dried is introduced near the bottom of the casing at 25, and diffuses 50 upwardly through the column, becoming dried. The dried uid is removed at 2li.y Liquefled caustic drips -down and collects in the sump or reservoir part of the casing, as shown at 21. It is rempved bya conduit 28.

At ordinary temperatures of operation, say 20 to 30 C., the specific gravity of the caustic liquor leaving the solid mono-hydrate is around 1.5, corresponding to a 50 per cent NaOI-I solution.

At higher-working temperatures than this, the e0 NaOH becomes .liquid enough to flow away at a somewhat higher concentration, and viceversa. In the case of any particular liquid to be dried, f

if .its specific gravity is above about 1.5 the ap` paratus will be of the general type' shown in Fig. 05

1; if below 1.5, the apparatus of Fig. 2 is employed." Liquids of markedly different density than that of the caustic liquor make possible higher ow rates than in the case of liquidsv of ticularlysuitable for dryingecarbon tetrachloride 75 density differing but littfe from that of the spent 70 caustic liquor. But the process operates satis` 3 is especially compact. The drying capacity,y

a both as regards ultimate amount of moisture recasing 30 is `provided having a conical sump bot-y tom 3|, and a distributor il for CC14 at the top.

The casing is partly filled with shapes of mono'- hydrated NaOH (about 70 per cent NaOH) supported on a pervious grid I2 as in Fig. -l. In the lower portion of the casing is a collecting cone" 32 with a discharge pipe 33 at its top. An outlet pipe 34 dischargesfrom the sump bottom 3I.

In operation; C014v introduced -at Il and caused to trickle down over the mono-hydrate spheres. Liqueed caustic likewise drains down as it forms. In the sump bottom the droplets of'CCl4 coalesce to form a body of C014, indicated at 3 5, and the lighter droplets of NaOH solution rise and form a supernatant pool or body, indicated at 36. NaOH solution and CCli are re'- moved at 33 and '34 respectively. V'Ihe top or highest part of outlet pipe 34 is arranged at such height as to maintain the desiredliquid level, as shown. Fresh mono-hydrate lumps are intro-v duced through tubes 3l as required.

In the apparatus of Fig. 3 the caustic bodies.

are not submerged in liquid. The CC14 tends to distribute itself filmwise over the lumps and ex-A cellent contact is assured. In employing mono-hydrated caustic 'soda on supporting bodies, such as Raschig rings, re-

charging of the drying apparatus is carried out in a somewhat different manner. The rings are left permanently in the towerand when it 'is de- Caustic potash may be used in the present invention in lieu of caustic soda, although it is not as emcient, poundl for pound, because .of the.

higher molecular weight. In using it a caustic potash liquor is brought to such a concentration that it will set on cooling and remain solid up to- 60-80 C., melting again at'higher temperature.

Mixtures of KOI-I and NaOH hydrates have inv teresting properties in this connection since -for equivalent melting points, dehydration can be carried furtherand alower vapor tension oband other dense liquids. The. apparatus of Fig.

This matter is described in detail in to expose fresh surfaces of alkali to the flowing fluid.

tained while still making a. material solid at 60-80C.

What I claim is:

s 1. In drying Hnocontaining fluids which are substantially inert chemically with respect to caustic soda, the process which comprises bringing` said fluid in contact with extensive surfaces water and-arranged for free drainage, whereby the Ahydrated caustic soda liqueiies upon taking up' moisture from-the f luid, and removing the liquefied caustic soda as it is formed to expose 'fresh surfaces of solid hydrated caustic soda to the fluid.A

.2. The process of 'claim 1 wherein the hydrated caustic sodacorresponds substantially to the monohydrate NaOHHzO.

of solid` hydrated causticsoda containing 66 to i` 80 per cent NaOH and 34 to 20 per centcombined 3. The process of claim 1 wherein the fluid is a.

gas, and the lliquefied. caustic soda flows down- 4. The process of man 1 wherein the num is carbon tetrachloride, and the liquefied caustic soda formed is displaced upwardly by the heavier tetrachloride.

`5. The process of claim 1 wherein the solid hydrated caustic soda is in the form of balls.

6. A methodiof drying moist iuidsv whichf are extensive surfaces of solid hydrated caustic soda containing about 66 to 80 per cent NaOH and 34 to 20 per cent combined water and arranged for freeliquid'drainage past the surfaces, where- 'by the hydrated caustic soda liquefles upon taking up moisture from the uid, and removing the liquefied caustic soda as it is formed', by gravitational action, to expose fresh surfaces of solid hydratedcaustic soda to thefiowing iluid.

7. A method of drying moist fluids which are inert chemically .with respect t'o caustic alkalis,

comprising passing a flow of the fluid past extensive surfaces of caustic alkali hydrated suicentvly to have am'elting point of 60 to 80 C. and

arranged for'. free liquid drainage from the surfaces, whereby the hydrated caustic liqueies )upon taking up moisture from'the fluid, andre- Max-neuron. 1 

